EP3088563B1 - Substrat traité en surface et procédé de traitement de surface pour celui-ci - Google Patents
Substrat traité en surface et procédé de traitement de surface pour celui-ci Download PDFInfo
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- EP3088563B1 EP3088563B1 EP14874603.5A EP14874603A EP3088563B1 EP 3088563 B1 EP3088563 B1 EP 3088563B1 EP 14874603 A EP14874603 A EP 14874603A EP 3088563 B1 EP3088563 B1 EP 3088563B1
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- color
- film
- wavelength conversion
- conversion layer
- metal matrix
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- 238000000034 method Methods 0.000 title claims description 30
- 238000004381 surface treatment Methods 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 claims description 78
- 239000002184 metal Substances 0.000 claims description 78
- 239000011159 matrix material Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 229910052749 magnesium Inorganic materials 0.000 claims description 36
- 239000011777 magnesium Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 32
- 238000007654 immersion Methods 0.000 claims description 28
- 239000011651 chromium Substances 0.000 claims description 26
- 150000002739 metals Chemical class 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 11
- 239000000347 magnesium hydroxide Substances 0.000 claims description 11
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- -1 aluminum (Al) Chemical class 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 230000014509 gene expression Effects 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 238000007737 ion beam deposition Methods 0.000 claims description 2
- 238000007733 ion plating Methods 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 61
- 239000000243 solution Substances 0.000 description 47
- 238000004040 coloring Methods 0.000 description 18
- 239000003086 colorant Substances 0.000 description 16
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- 238000000576 coating method Methods 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 4
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- 230000001939 inductive effect Effects 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
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- 239000007791 liquid phase Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/64—Treatment of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/324—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
Definitions
- the present invention relates to a color-treated substrate having excellent corrosion resistance and for developing a color on a surface thereof, and a substrate color treatment method therefor.
- Magnesium is a metal which belongs to lightweight metals among practical metals, has excellent wear resistance, and is very resistant to sunlight and eco-friendly, but has a difficulty in realizing a metal texture and various colors. Further, since it is a metal having the lowest electrochemical performance and is highly active, when a color treatment is not performed thereon, it may be quickly corroded in air or in a solution, and thus has a difficulty in industrial application.
- Korean Patent Laid-open Publication No. 2011-0016750 disclosed a PVD-sol gel method of performing sol-gel coating after dry coating a surface of a substrate formed of a magnesium alloy with a metal-containing material in order to realize a metal texture and ensure corrosion resistance
- Korean Patent Laid-open Publication No. 2011-0134769 disclosed an anodic oxidation method of imparting gloss to a surface of a substrate including magnesium using chemical polishing and coloring a surface by anodic oxidation of the substrate in an alkaline electrolyte including a pigment dissolved therein.
- JP 2010 265522 A discloses a method of protecting a coloring metal and a coloring metal having an interference color-expression layer by an oxide film which can obtain a coloring metal having excellent stain resistance and adhesion.
- GB 532 878 A and US 2 250 473 A disclose methods of producing colored corrosion-resistant coatings upon articles of magnesium by immersing in an aqueous alkaline solution containing the dye.
- the PVD-sol gel method has a problem in that a texture realized on the surface of the substrate is not the intrinsic texture of magnesium although a metal texture may be realized on the surface of the substrate, and the realization of a variety of colors is difficult. Furthermore, when a color treatment is performed using the anodic oxidation method, there is a problem in that an opaque oxide film is formed on the surface of the substrate, and the realization of the intrinsic texture of metals is not easy.
- An objective of the present invention is to provide a color-treated substrate having excellent corrosion resistance and for developing a color on a surface thereof.
- Another objective of the present invention is to provide a substrate surface treatment method therefor.
- an embodiment of the present invention provides a color-treated substrate which has the intrinsic texture of metals, including:
- Another embodiment of the present invention provides a method of color-treating a substrate which has the intrinsic texture of metals, including:
- the color-treated substrate according to the present invention not only can improve corrosion resistance, but also can uniformly develop a color on a surface by including a film having a uniform thickness on a metal matrix. Further, scratch resistance and durability of the substrate can be improved without a change in a color developed on the film by sequentially including a wavelength conversion layer and a top coat on the film.
- FIG. 1 shows images illustrating a thickness of a film according to immersion time, which is measured using a transmission electron microscope in an embodiment: where A shows a substrate in accordance with the immersion time of 10 minutes; B shows a substrate in accordance with the immersion time of 170 minutes; and C shows a substrate in accordance with the immersion time of 240 minutes.
- FIG. 2 is an image showing a color-treated substrate including a chromium (Cr) layer, which is taken by a transmission electron microscope in an embodiment: where D1 is a thickness of a chromium layer, and the value thereof is about 10 nm.
- Cr chromium
- FIG. 3 is an image showing a color-treated substrate including an aluminum (Al) layer, which is taken by a transmission electron microscope in an embodiment: where D2 is a thickness of an aluminum layer, and the value thereof is about 13 nm.
- Color coordinates refer to coordinates in a CIE color space, including color values defined by the Commission International de l'Eclairage (CIE), and any position in the CIE color space may be expressed as three coordinate values of L*, a* and b*.
- CIE Commission International de l'Eclairage
- an L* value represents brightness.
- an a* value represents whether a color at a corresponding color coordinate leans toward a pure magenta color or a pure green color
- a b* value represents whether a color at a corresponding color coordinate leans toward a pure yellow color or a pure blue color.
- the a* value ranges from -a to +a
- the maximum a* value (a* max) represents a pure magenta color
- the minimum a* value (a* min) represents a pure green color.
- a* value when an a* value is negative, a color leans toward a pure green color, and when an a* value is positive, a color leans toward a pure magenta color.
- the b* value ranges from -b to +b.
- the maximum b* value (b* max) represents a pure yellow color
- the minimum b* value (b* min) represents a pure blue color.
- b* max represents a pure yellow color
- b* min represents a pure blue color.
- a "wavelength conversion layer” refers to a layer for controlling a wavelength of incident light by adjusting reflection, refraction, scattering or diffraction of light, which may serve to minimize additional refraction and scattering, in a top coat, of light refracted and scattered in a film, and maintain a color developed by the layer by inducing light reflection.
- a unit “T”, as used herein, represents a thickness of a substrate including magnesium, and is the same as a unit “mm”.
- the present invention provides a color-treated substrate and a substrate surface treatment method therefor.
- a PVD-sol gel method or an anodic oxidation method which is a method of coating a surface of a material with a metal-containing material or a pigment has been conventionally known as a method for realizing a color on the material including magnesium.
- these methods may cause a reduction in durability of the substrate.
- the present invention suggests a color-treated substrate prepared by sequentially stacking a wavelength conversion layer and a top coat after immersing a metal matrix in a hydroxide solution.
- the substrate according to the present invention has an advantage in that a uniform color is developed on a substrate surface and scratch resistance and durability of the substrate may be improved by sequentially including a film, a wavelength conversion layer and a top coat on a metal matrix.
- An embodiment of the present invention provides a color-treated substrate according to claim 1.
- the color-treated substrate according to the present invention includes a film on the metal matrix and has a structure in which a wavelength conversion layer and a top coat are sequentially stacked on the film.
- This stacked structure may be formed on one or both surfaces of the metal matrix.
- the film is formed on the metal matrix and serves to develop a color
- the top coat which is the outermost layer, functions to improve scratch resistance and durability of the substrate, but when only the film and top coat are formed on the metal matrix, there is a problem in that a color developed by the film is changed due to the top coat.
- the color-treated substrate according to the present invention prevents discoloration due to the top coat by forming a wavelength conversion layer between the film and the top coat.
- the wavelength conversion layer minimizes additional refraction and scattering, in the top coat, of light, refracted and/or scattered in the film, and maintains a color developed by the film by inducing light reflection.
- the wavelength conversion layer includes one or more selected from the group consisting of metals including aluminum (Al), chromium (Cr), titanium (Ti), gold (Au), molybdenum (Mo), silver (Ag), manganese (Mn), zirconium (Zr), palladium (Pd), platinum (Pt), cobalt (Co), cadmium (Cd) or copper (Cu) and ions thereof, and specifically, may include chromium (Cr).
- the metals may be in the form of metal particles, and may include various types such as a metal nitride, a metal oxide or a metal carbide by reacting with a nitrogen gas, an ethane gas or an oxygen gas in the process of forming the wavelength conversion layer.
- the wavelength conversion layer may be a continuous layer in which the metals are densely stacked on the film and fully cover the surface of the film, or a discontinuous layer in which the metals are dispersed on the film.
- the wavelength conversion layer has an average thickness which can prevent a change in color developed by the film.
- the average thickness satisfies a condition in the range of 5 to 200 nm. More specifically, the average thickness is in the range of 5 to 150 nm, 10 to 100 nm, 5 to 20 nm, 10 to 15 nm, 20 to 40 nm, 10 to 30 nm, or 30 to 50 nm.
- the substrate has a structure in which a film, a wavelength conversion layer and a top coat are sequentially stacked on a metal matrix. Further, as a result of transmission electron microscope imaging of the color-treated substrate according to the present invention which contains chromium (Cr) or aluminum (Al), it can be determined that the average thickness of each wavelength conversion layer is about 10 nm and 13 nm, respectively.
- an average color coordinate deviation ( ⁇ L*, ⁇ a*, ⁇ b*) of each point may satisfy one or more conditions of ⁇ L* ⁇ 0.5, ⁇ a* ⁇ 0.7 and ⁇ b* ⁇ 0.6.
- the color-treated substrate according to the present invention may satisfy two or more of the conditions, and more specifically, may satisfy all the conditions.
- a sample with a size of 1 cm ⁇ 1 cm as a metal matrix was immersed in a 10 wt% NaOH solution at 100 °C for 85 minutes, a wavelength conversion layer and a top coat were sequentially formed thereon, and then the color coordinates in a CIE color space of any three points which are present on the sample were measured.
- the results of color coordinate deviations were respectively 0.14 ⁇ L* ⁇ 0.34, 0.02 ⁇ a* ⁇ 0.34 and 0.34 ⁇ b* ⁇ 0.40, all of which satisfy the conditions.
- the ⁇ E* derived from the measured values was determined as 0.424 ⁇ E* ⁇ 0.578, which indicates a significantly small value of color coordinate deviation. This shows that the color-treated substrate according to the present invention has a uniform color (refer to Experimental Example 3).
- the film includes one or more of sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ) and barium hydroxide (Ba(OH) 2 ), and more specifically, may include magnesium hydroxide (Mg(OH) 2 ) (refer to Experimental Example 2).
- an average thickness of the film is specifically in the range of 50 nm to 2 ⁇ m, and more specifically, in the range of 100 nm to 1 ⁇ m.
- a color is realized on the color-treated substrate according to the present invention using the nature of light incident to a substrate surface, and a uniform color is realized by uniformly forming the film for scattering and refracting light incident to the substrate surface.
- a desired color is realized without loss of the intrinsic texture of metals of the substrate within the above-described range.
- the type or form of a metal matrix containing magnesium of the color-treated substrate is not particularly limited.
- a magnesium substrate formed of magnesium; a stainless steel or titanium (Ti) substrate of which a surface has magnesium dispersed therein may be used.
- a clear coating agent for forming a top coat of the color-treated substrate is not particularly limited as long as it is a clear coating agent which is applicable to coatings of metals, metal oxides or metal hydroxides. More specifically, a matte clear coating agent or a glossy/matte clear coating agent which is applicable to metal coatings may be exemplified as the clear coating agent.
- Another embodiment of the present invention provides a method of color-treating a substrate accordinging to claim 4.
- the step of forming the film on the metal matrix is a step for realizing a color on a metal matrix.
- the color is realized by the film formed on the metal matrix, and the film is uniformly formed by immersing the metal matrix in the hydroxide solution.
- a solution having one or more selected from the group consisting of NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 and Ba(OH) 2 dissolved therein is used.
- the coloring speed, the coloring power and the color uniformity of the metal matrix containing magnesium were evaluated.
- a solution in which NaOH had been dissolved was used as a hydroxide solution
- the coloring speed thereof was four times faster as compared to that of the case in which distilled water was used.
- the coloring power of the color developed on the surface was excellent, and a uniform color was realized.
- a solution in which a metal hydroxide such as NaOH is dissolved is used as a hydroxide solution, the film is uniformly formed on the surface of the metal matrix in a short time, and thus a color may be realized by excellent coloring power (refer to Experimental Example 1).
- the preparation method according to the present invention may control the thickness of the film formed on the surface of the matrix according to immersion conditions.
- the thickness of the films formed on matrices may be different even though the matrices were immersed under the same conditions. Accordingly, it is preferable to control the thickness of the film by adjusting immersion conditions according to the thickness of the matrix containing magnesium.
- the concentration of the hydroxide solution may range from 1 to 80 wt%, and more specifically, from 1 to 70 wt%; 5 to 50 wt%; 10 to 20 wt%; 1 to 40 wt%; 30 to 60 wt%; 15 to 45 wt%; or 5 to 20 wt%.
- the temperature of the hydroxide solution may range from 90 to 200 °C, more specifically, from 100 to 150 °C, and even more specifically, from 95 to 110 °C.
- the immersion time may be in the range of 1 to 500 minutes, and specifically, in the range of 10 to 90 minutes. In the present invention, various colors may be economically realized on the surface of the substrate within the above-described ranges.
- the color realized on the surface of the substrate may be adjusted by controlling the concentration and temperature of the hydroxide solution for immersing the matrix and the immersion time (refer to Experimental Example 2).
- the step of forming the film on the metal matrix may include: a first immersion step of immersing in a hydroxide solution with a concentration of N1; and an nth immersion step of immersing in a hydroxide solution with a concentration of Nn, and the first immersion step and the nth immersion step may be carried out using a method in which the concentration of the hydroxide solution satisfies the following Expressions 1 and 2 independently of each other, and n is an integer of 2 or more and 6 or less: 8 ⁇ N 1 ⁇ 25
- the step of forming the film on the metal matrix is a step of realizing a color on the surface of the metal matrix, and the developed color may be controlled by adjusting the thickness of the formed film.
- the thickness of the film may be controlled according to the concentration of the hydroxide solution, when the concentration of the hydroxide solution for immersing the matrix is divided into N 1 to N n , and specifically, N 1 to N 6 ; N 1 to N 5 ; N 1 to N 4 ; N 1 to N 3 ; or N 1 to N 2 ; and the matrix is sequentially immersed therein, minute differences in the color realized on the surface may be controlled.
- the method of surface-treating the substrate according to the present invention may further include one or more steps of:
- the step of pretreating the surface is a step of eliminating contaminants remaining on the surface by treating the surface using an alkaline cleaning solution or grinding the surface before immersing the metal matrix in the hydroxide solution.
- the alkaline cleaning solution is not particularly limited as long as the solution is generally used to clean a surface of metals, metal oxides or metal hydroxides in the related field.
- the grinding may be performed by buffing, polishing, blasting or electrolytic polishing, but is not limited thereto.
- the present step not only contaminants or scale which is present on the surface of the matrix containing magnesium may be removed, but also the speed of forming the film may be controlled by surface energy of the surface and/or surface conditions, specifically, microstructural changes of the surface.
- the thickness of the film formed on the polished matrix may be different from that of the film formed on the unpolished matrix even though the film is formed on the polished matrix under the same conditions as the film of the unpolished matrix, and each color developed on the surface may be different accordingly.
- the step of rinsing is a step of eliminating any hydroxide solution remaining on the surface by rinsing the surface after the step of immersing the metal matrix in the hydroxide solution. In this step, additional formation of the film due to any remaining hydroxide solution may be prevented by removing the hydroxide solution remaining on the surface of the matrix.
- the step of forming the wavelength conversion layer is a step of forming a wavelength conversion layer which is capable of preventing a color developed by a film from being changed due to a top coat.
- the degree of discoloring may vary according to the average thickness of the top coat. For example, when the average thickness of the top coat is in the range of 5 to 20 ⁇ m, a color may be changed to brown, and when the average thickness of the top coat is 30 ⁇ m or more, a color may be changed to black.
- the wavelength conversion layer prevents a change in a color developed by the film by minimizing refraction and scattering of the color-developing light due to the top coat and inducing light reflection.
- the wavelength conversion layer may be formed by a method which is generally used to form a wavelength conversion layer in the related field. Specifically, it may be formed by a method such as vacuum deposition, sputtering, ion plating or ion beam deposition.
- the wavelength conversion layer maintains a color developed by the film by minimizing additional refraction and scattering of the color-developing light due to the top coat and reflecting the light.
- the wavelength conversion layer includes one or more metals selected from the group consisting of metals including aluminum (Al), chromium (Cr), titanium (Ti), gold (Au), molybdenum (Mo), silver (Ag), manganese (Mn), zirconium (Zr), palladium (Pd), platinum (Pt), cobalt (Co), cadmium (Cd) or copper (Cu) and ions thereof.
- the step of forming the top coat on the wavelength conversion layer is a step of introducing a top coat on a wavelength conversion layer using a matte or glossy/matte clear coating agent so as to improve scratch resistance and durability of a substrate.
- the top coat may be formed by a method which is generally used to form a top coat on a wavelength conversion layer in the related field.
- a magnesium-containing sample with a size of 1 cm ⁇ 1 cm ⁇ 0.4 T as a metal matrix was degreased by immersing in an alkaline cleaning solution, and the degreased sample was immersed in a 10 wt% NaOH solution at 100 °C for 50 minutes. Thereafter, the sample was rinsed using distilled water and dried in a drying oven, and a chromium (Cr) layer having a thickness in the range of 10 to 20 nm was formed using a sputtering method.
- the chromium (Cr) layer was coated with a matte clear coating material in a liquid phase, and dried in an oven at 120 to 150 °C to prepare a color-treated magenta sample.
- an average thickness of a matte clear coating layer was 25 ⁇ m.
- a color-treated green sample was prepared in the same manner as in Example 1 except that the sample was immersed for 85 minutes instead of 50 minutes.
- a color-treated silver sample was prepared in the same manner as in Example 1 except that the sample was immersed for 10 minutes instead of 50 minutes. Transmission electron microscope imaging was performed on the prepared sample, and the result is shown in FIG. 2 . As shown in FIG. 2 , it was determined that an average thickness D1 of a chromium layer formed on the sample was about 10 nm.
- a color-treated silver sample was prepared in the same manner as in Example 1 except that the sample was immersed for 10 minutes instead of 50 minutes and an aluminum (Al) layer was formed instead of a chromium (Cr) layer. Transmission electron microscope imaging was performed on the prepared sample, and the result is shown in FIG. 3 . As shown in FIG. 3 , it was determined that an average thickness D2 of an aluminum layer formed on the sample was about 13 nm.
- a magnesium-containing sample with a size of 1 cm ⁇ 1 cm ⁇ 0.4 T as a metal matrix was degreased by immersing in an alkaline cleaning solution, and the degreased sample was immersed in a 10 wt% NaOH solution at 100 °C for 85 minutes. Thereafter, the sample was rinsed using distilled water, dried in a drying oven, and coated with a matte clear coating material in a liquid phase, and dried in an oven at 120 to 150 °C to prepare a color-treated sample.
- an average thickness of a matte clear coating layer was 5 ⁇ m.
- a color-treated sample was prepared in the same manner as in Comparative Example 1 except that coating was performed such that an average thickness of a matte clear coating layer was 30 ⁇ m instead of 5 ⁇ m.
- Magnesium-containing samples with a size of 1 cm ⁇ 1 cm ⁇ 0.4 T as a metal matrix were degreased by immersing in an alkaline cleaning solution, and the degreased samples each were immersed in a 10 wt% NaOH solution at 100 °C for 40 minutes, 1 hour and 2 hours, respectively. Thereafter, the sample was rinsed using distilled water and dried in a drying oven, and colors developed on the surface were evaluated with the naked eye.
- the sample prepared by immersing in a 10 wt% NaOH solution has a faster coloring speed in comparison with that of a sample prepared by immersing in distilled water as a hydroxide solution. More specifically, the sample prepared by immersing in a 10 wt% NaOH solution was colored to have a silver color after 10 minutes of immersion, and changed to a yellow color, and then colored to have an orange color within 40 minutes. However, in the case of the sample of which the immersion time was 40 minutes, it was determined that a color change amount of the surface was slight and a color difference was not so large as compared to a non-color-treated substrate, and the sample of which the immersion time was 1 hour was gradually colored to have a yellow color. Further, the sample of which the immersion time was 2 hours was colored to have a yellow color, but the coloring power of the developed color was significantly lower than that of the sample prepared by immersing in a 10 wt% NaOH solution.
- a magnesium-containing sample with a size of 1 cm ⁇ 1 cm ⁇ 0.4 T as a metal matrix was degreased by immersing in an alkaline cleaning solution, and the degreased sample was immersed in a 10 wt% NaOH solution at 100 °C for 240 minutes.
- a developed color was observed with the naked eye at intervals of 5 to 10 minutes immediately after the sample was immersed in the NaOH solution.
- TEM transmission electron microscope
- the color-treated substrate according to the present invention was determined to have a developed color varying according to the time of immersion in the hydroxide solution. More specifically, when the non-color-treated sample having a silver color was immersed in the hydroxide solution, it was determined that yellow, orange, red, purple, blue and green colors were sequentially developed after 30 minutes of immersion, and this color change becomes repeated at a predetermined interval over time.
- the average thickness of the film is increased to about 200 nm, 600 nm and 900 nm as each immersion time has passed.
- the color-treated substrate according to the present invention realizes coloring by including the film containing magnesium hydroxide (Mg(OH) 2 ). Further, it can be seen that the thickness of the film formed on the surface may be controlled according to the immersion time of the metal matrix containing magnesium, and the color developed therefrom may be controlled.
- Mg(OH) 2 magnesium hydroxide
- a color developed by the film is maintained after forming the top coat by including the wavelength conversion layer in the case of the color-treated substrate according to the present invention. More specifically, it was determined that colors realized on the surface by the film were respectively magenta and green colors before forming the wavelength conversion layer in Examples 1 and 2, and colors of the surfaces were not changed although the wavelength conversion layers and top coats were sequentially formed afterward. In contrast, in the case of Comparative Examples 1 and 2, it was determined that colors realized on the surface by the film were respectively magenta and green colors before forming the top coat, but the colors realized on the surface were changed when the top coat was formed on the film. Here, the colors were respectively changed to brown and black colors in accordance with the thickness of the top coat.
- a wavelength conversion layer minimizes additional refraction and scattering of color-developing light and realizes light reflection to prevent discoloration in the case of the samples of examples in which the wavelength conversion layer is formed between the film and top coat.
- the color-treated substrate according to the present invention has a uniformly developed color. More specifically, the average color coordinate deviation of any three points existing on the sample were determined as 0.14 ⁇ L* ⁇ 0.34, 0.02 ⁇ a* ⁇ 0.34 and 0.34 ⁇ b* ⁇ 0.40 and 0.424 ⁇ E* ⁇ 0.578 in the case of the sample of Example 2 which includes a wavelength conversion layer. This indicates that a color of color-treated magnesium according to the present invention was uniformly developed.
- the color-treated substrate according to the present invention may uniformly realize a color by including a film having a uniform thickness on a metal matrix. Further, scratch resistance and durability of the substrate may be improved without a change in a color developed on the film by sequentially including a wavelength conversion layer and a top coat on the film.
- the color-treated substrate according to the present invention not only can improve corrosion resistance, but also can uniformly develop a color on a surface by including a film having a uniform thickness on a metal matrix. Further, scratch resistance and durability of the substrate can be improved without a change in a color developed on the film by sequentially including a wavelength conversion layer and a top coat on the film, and thus the color-treated substrate according to the present invention can be usefully used in the fields of building exterior materials, automobile interiors, and particularly electrical and electronic component materials, such as mobile phone case components, in which a magnesium material is used.
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Claims (10)
- Substrat à traitement de couleur qui présente la texture intrinsèque de métaux, comprenant :une matrice de métal contenant du magnésium ;un film formé sur la matrice et contenant un composé représenté par la Formule chimique 1 ci-après ;une couche de conversion de longueur d'onde formée sur le film ; etun revêtement supérieur formé sur la couche de conversion de longueur d'onde,sachant que la couche de conversion de longueur d'onde inclut un ou plusieurs éléments sélectionnés dans le groupe constitué par des métaux incluant l'aluminium (Al), le chrome (Cr), le titane (Ti), l'or (Au), le molybdène (Mo), l'argent (Ag), le manganèse (Mn), le zirconium (Zr), le palladium (Pd), le platine (Pt), le cobalt (Co), le cadmium (Cd) ou le cuivre (Cu) et des ions de ceux-ci,sachant qu'une épaisseur moyenne du film est comprise dans une plage de 50 nm à 2 µm,sachant qu'une épaisseur moyenne de la couche de conversion de longueur d'onde est comprise dans une plage de 5 à 200 nm :
[Formule chimique 1] M(OH)m
où M inclut un ou plusieurs éléments sélectionnés dans le groupe constitué par Na, K, Mg, Ca et Ba, et m est 1 ou 2. - Le substrat à traitement de couleur selon la revendication 1, sachant que, en trois points quelconques inclus dans une zone arbitraire d'une largeur de 1 cm et d'une longueur de 1 cm qui est présente sur le revêtement supérieur, un écart de coordonnées de couleur moyenne (ΔL*, Δa*, Δb*) de chaque point satisfait à une ou plusieurs conditions de ΔL* < 0,5, Δa* < 0,7 et Δb* < 0,6.
- Le substrat à traitement de couleur selon la revendication 1, sachant que la matrice de métal inclut en outre de l'acier inoxydable ou du titane (Ti).
- Procédé de traitement de couleur d'un substrat qui présente la texture intrinsèque de métaux, comprenant :une étape de formation d'un film contenant un composé représenté par la Formule chimique 1 ci-après sur une matrice de métal contenant du magnésium ;une étape de formation d'une couche de conversion de longueur d'onde sur le film ; etune étape de formation d'un revêtement supérieur sur la couche de conversion de longueur d'onde,sachant que la couche de conversion de longueur d'onde inclut un ou plusieurs éléments sélectionnés dans le groupe constitué par des métaux incluant l'aluminium (Al), le chrome (Cr), le titane (Ti), l'or (Au), le molybdène (Mo), l'argent (Ag), le manganèse (Mn), le zirconium (Zr), le palladium (Pd), le platine (Pt), le cobalt (Co), le cadmium (Cd) ou le cuivre (Cu) et des ions de ceux-ci,sachant qu'une épaisseur moyenne du film est comprise dans une plage de 50 nm à 2 µm,sachant qu'une épaisseur moyenne de la couche de conversion de longueur d'onde est comprise dans une plage de 5 à 200 nm,
[Formule chimique 1] M(OH)m
où M inclut un ou plusieurs éléments sélectionnés dans le groupe constitué par Na, K, Mg, Ca et Ba, et m est 1 ou 2. - Le procédé selon la revendication 4, sachant que le film est formé par immersion de la matrice de métal contenant du magnésium dans une solution d'hydroxyde à l'étape de formation du film sur la matrice de métal contenant du magnésium.
- Le procédé selon la revendication 5, sachant que la solution d'hydroxyde inclut un ou plusieurs composés sélectionnés dans le groupe constitué par NaOH, KOH, Mg(OH)2, Ca(OH)2 et Ba(OH)2.
- Le procédé selon la revendication 6, sachant qu'une concentration de la solution d'hydroxyde est comprise dans une plage de 1 à 80 % en poids.
- Le procédé selon la revendication 5, sachant que
l'étape de formation du film sur la matrice de métal contenant du magnésium inclut :une première étape d'immersion dans une solution d'hydroxyde à une concentration de N1 ; etune nième étape d'immersion dans une solution d'hydroxyde à une concentration de Nn,où N1 et Nn représentent une concentration d'une solution d'hydroxyde à chaque étape, et ont des unités de % en poids. - Le procédé selon la revendication 4, sachant que l'étape de formation de la couche de conversion de longueur d'onde est effectuée par dépôt sous vide, pulvérisation, placage ionique ou dépôt par faisceau ionique.
- Le procédé selon la revendication 4, comprenant en outre une ou plusieurs étapes de :prétraitement d'une surface avant l'étape de formation du film sur la matrice de métal contenant du magnésium ; etrinçage après l'étape de formation du film sur la matrice de métal.
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PCT/KR2014/012917 WO2015099496A1 (fr) | 2013-12-26 | 2014-12-26 | Substrat traité en surface et procédé de traitement de surface pour celui-ci |
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US11751349B2 (en) | 2019-05-28 | 2023-09-05 | Apple Inc. | Anodized part having a matte black appearance |
US11614778B2 (en) | 2019-09-26 | 2023-03-28 | Apple Inc. | Anodized part having low reflectance of visible and near-infrared light |
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KR101765906B1 (ko) * | 2010-08-19 | 2017-08-07 | 엘지이노텍 주식회사 | 아노다이징을 이용한 회로기판 및 그 제조 방법 |
KR101238895B1 (ko) * | 2010-12-28 | 2013-03-04 | 재단법인 포항산업과학연구원 | 표면 조직이 치밀한 마그네슘 합금 및 그 표면 처리 방법 |
JP5705054B2 (ja) * | 2011-07-26 | 2015-04-22 | 独立行政法人産業技術総合研究所 | マグネシウム合金材、およびマグネシウム合金の表面処理方法 |
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Publication number | Publication date |
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EP3088565B1 (fr) | 2019-06-12 |
EP3088565B9 (fr) | 2019-10-23 |
EP3088563A1 (fr) | 2016-11-02 |
CN105849313A (zh) | 2016-08-10 |
EP3088565A4 (fr) | 2017-03-08 |
CN105849314A (zh) | 2016-08-10 |
EP3088564B1 (fr) | 2019-05-22 |
EP3088562A1 (fr) | 2016-11-02 |
CN105849315A (zh) | 2016-08-10 |
EP3088562B1 (fr) | 2019-05-08 |
EP3088566A4 (fr) | 2017-03-08 |
EP3088563A4 (fr) | 2017-03-08 |
EP3088566B1 (fr) | 2018-08-15 |
EP3088566A1 (fr) | 2016-11-02 |
EP3088564A1 (fr) | 2016-11-02 |
EP3088564A4 (fr) | 2017-03-08 |
CN105849313B (zh) | 2018-03-09 |
EP3088565A1 (fr) | 2016-11-02 |
EP3088562A4 (fr) | 2017-03-08 |
CN105849314B (zh) | 2018-06-26 |
CN105849315B (zh) | 2018-09-21 |
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